US3996068A - Primary dry cell - Google Patents
Primary dry cell Download PDFInfo
- Publication number
- US3996068A US3996068A US05/583,920 US58392075A US3996068A US 3996068 A US3996068 A US 3996068A US 58392075 A US58392075 A US 58392075A US 3996068 A US3996068 A US 3996068A
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- United States
- Prior art keywords
- dry cell
- electrolyte
- magnesium
- cathode depolarizer
- zinc
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/04—Cells with aqueous electrolyte
- H01M6/06—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
Definitions
- the present invention relates to improvements in primary dry cells. More particularly, the present invention relates to primary dry cells employing a zinc anode and an electrolyte consisting essentially of an aqueous solution containing a metallic salt of a halogen-containing acid especially, though not exclusively, a zinc salt such as zinc chloride.
- Primary dry cells are composed essentially of a consumable metal anode, a cathode depolarizer usually manganese dioxide and an electrolyte.
- the familiar Leclanche primary dry cell conventionally used as the power source in flashlights and other portable electric devices, comprises a zinc anode, a cathode depolarizer mix cake containing manganese dioxide and a conductive material such as carbon black or graphite, and an electrolyte consisting of an aqueous solution of zinc chloride and ammonium chloride (i.e. sal ammoniac).
- Various inhibitors such as mercuric chloride, chromates, etc. may also be used in relatively small amounts within the electrolyte.
- the magnesium dry cell comprises a magnesium anode, a cathode depolarizer mix cake containing manganese dioxide and a conductive material and an electrolyte.
- the electrolyte consists essentially of an aqueous solution containing a magnesium salt such as magnesium chloride, magnesium perchlorate or magnesium bromide.
- the magnesium dry cell offers a number of important advantages over the conventional Leclanche dry cell. Some of these advantages are (1) a higher working voltage of between about 1.5 and 1.6 volts, (2) a considerably higher service capacity, i.e. hours of service on discharge per unit of weight and volume, and (3) superior shelf life particularly at high temperature storage.
- magnesium dry cell Another problem encountered with the magnesium dry cell is that of gas generation.
- the magnesium dry cell when on discharge generates hydrogen copiously due to reactivity of the working magnesium anode with water. It is therefore necessary to use costly resealable mechanical vents which will vent the hydrogen gas formed on discharge and yet prevent loss of moisture and ingress of air on shelf storage.
- one of the major drawbacks of the magnesium dry cell lies in the fact that magnesium is an expensive raw material and consequently the manufacturing cost of the magnesium cell is high.
- Another object of the present invention is to provide certain improvements in primary dry cells. More specifically, another object of the present invention is to provide a primary dry cell system which effectively circumvents the problems encountered with the magnesium dry cell while at the same time retaining some of its advantages. Still another object of the present invention is to provide a primary dry cell system having a high service capacity.
- a primary dry cell system comprising a zinc anode, a cathode depolarizer mix cake containing a mixture of manganese dioxide and an electrolyte absorptive conductive material and an inner electrolyte consisting essentially of an aqueous solution containing a metallic salt of a halogen-containing acid especially, though not exclusively, a zinc salt such as zinc chloride, the inner electrolyte constituting from about 60 to 71 percent by volume of the total cathode depolarizer mix cake.
- the term “inner electrolyte” is intended to denote the electrolyte normally incorporated within the cathode depolarizer mix cake.
- the term “outer electrolyte” as used herein and in the appended claims is intended to denote the electrolyte normally immobilized within the conventional separator interposed between the metal anode and cathode mix cake.
- the outer electrolyte may be immobilized with a suitable gelatinizing agent such as flour or starch to form a conventional paste separator or the separator medium may be one of the conventional film separators such as carboxymethylcellulose coated paper thoroughly wetted with the outer electrolyte.
- the present invention is predicated on the discovery which is an outgrowth of earlier experimental work with the magnesium dry cell, that a primary dry cell utilizing a zinc anode and an aqueous metallic halide or perchlorate salt electrolyte can be made having a high service capacity if the cathode mix formulation is devised using a high solution volume, i.e. percent by volume of inner electrolyte.
- a primary dry cell using an aqueous zinc chloride electrolyte for example, it has been found that during the electrochemical process which takes place on discharge, water is consumed or tied up in the form of a zinc hydroxide reaction product.
- This reaction product in turn will react with the zinc chloride electrolyte to form a hard, dense material having the formula ZnCl 2 .4Zn(OH) 2 . Because the cell does dry out on discharge, it has been found that the solution volume of the cathode depolarizer mix cake must be high enough to satisfy the above reaction and to insure electrolyte paths from the anode to cathode throughout the useful life of the cell.
- the cathode depolarizer mix is made in the usual manner by first dry blending particles of manganese dioxide, finely-divided conductive material such as acetylene black and optionally, minor amounts of various inhibitors, such as mercuric chloride. Conventionally, this blend is then wetted with the inner electrolyte to produce a uniformly moistened mix of a consistency suitable for molding to the shape of the cathode mix cake.
- cathode mix formula is devised using a high solution volume of between about 60 and 71 percent, a moldable mix of suitable consistency for forming the cathode depolarizer mix cake can be made which contains enough inner electrolyte to insure full service delivery.
- the ratio of manganese dioxide ore to carbon black should be fairly high in order to maintain the cell depolarization discharge capacity although a substantial percentage of the very highly absorbent carbon black is required in order to incorporate sufficient electrolyte. Ideally, it has been found that the ratio of manganese dioxide ore to carbon black should be maintained in the range of from about 4:1 to 9:1.
- the concentration of the electrolyte solution is another related factor. It has been found, for example, that a dry cell using a 6.0 normal solution of zinc chloride in water exhibits a slightly higher service capacity than a cell using a 9.8 normal electrolyte solution. This is believed due to the higher water content of the less concentrated electrolyte solution.
- electrolytes using several other salts are also useful in the practice of the present invention. It is possible, for example, to employ the same electrolyte solutions as used in the magnesium dry cell, i.e. magnesium chloride, magnesium perchlorate and magnesium bromide.
- the halogen-containing salt used in the electrolyte is a zinc salt such as zinc bromide and zinc chloride.
- the use of the zinc salt is preferred because it is more compatible with the zinc anode and thus anode corrosion problems are avoided.
- FIG. 1 is a vertical section of a primary dry cell embodying the present invention.
- FIG. 2 is a graph showing comparative discharge voltage curves.
- a cylindrical primary dry cell comprising a zinc cup or can 10 containing the cathode depolarizer mix cake 12 which is molded in the usual manner around a central carbon electrode rod 14 to form a conventional cathode bobbin.
- the cathode bobbin rests on a paper washer 16 in the bottom of the zinc cup or can 10 and is separated from the side walls of the zinc cup or can 10 by a thin film separator 18 such as carboxymethylcellulose coated paper or a methylcellulose separator.
- the dry cell is provided with a top seal 20 which may be made of wax or pitch poured onto the top of the bobbin washer 22 within the open end of the zinc cup or can 10.
- the thin film separator 18 is thoroughly wetted with the outer electrolyte which may be a concentrated solution of zinc chloride in water.
- the outer electrolyte is the same concentration as the inner electrolyte, e.g. 6.0 normal zinc chloride.
- a number of "AA" size primary dry cells were made using a zinc cup anode and an aqueous zinc chloride electrolyte, the construction of the cells being basically the same as that shown in FIG. 1.
- the cathode depolarizer mix cakes for each of the cells were molded from an electrolyte wetted mix prepared in the manner as described above and having the following formulation:
- the cathode depolarizer mix cake made with this formulation had approximately a 65 percent solution volume.
- the ratio of manganese dioxide ore to acetylene black in the formulation was 8.7:1.
- the real density of the wetted mix was 2.285 grams per cubic centimeter and the weight ratio of water in the electrolyte wetted mix to manganese dioxide ore in the mix was 0.460:1. This provided 1.65 grams of water per amperehour of manganese dioxide theoretical capacity.
- the cells made in the above example used a methylcellulose separator and the outer electrolyte was a 6.0 normal solution of zinc chloride in water.
- Curve 1 represents the continuous discharge of the "AA" size cells made in the above example on a 72 ohm load at 75° F.
- Curve 2 represents the discharge of a typical prior art Leclanche dry cell under the same drain conditions. It will be seen that the primary dry cells of the present invention exhibit a higher working voltage than the conventional Leclanche dry cells and that this voltage is sustained for a longer period of time. From these tests then, it is evident that the primary dry cells of the present invention possess a high service capacity.
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Primary Cells (AREA)
Abstract
Description
______________________________________ Cathode Mix % by Volume Ingredients % by Weight at 70° F. ______________________________________ Artificial MnO.sub.2 55.6 26.6 Acetylene black 6.4 8.0 Zn(OH).sub.2 (powder) 0.8 0.6 6.0 N ZnCl.sub.2 solution 37.2 64.8 Total 100.0 100.0 ______________________________________
Claims (3)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US05/583,920 US3996068A (en) | 1973-08-27 | 1975-06-05 | Primary dry cell |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US391611A US3888699A (en) | 1970-07-29 | 1973-08-27 | Primary dry cell |
US05/583,920 US3996068A (en) | 1973-08-27 | 1975-06-05 | Primary dry cell |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US391611A Division US3888699A (en) | 1970-07-29 | 1973-08-27 | Primary dry cell |
Publications (1)
Publication Number | Publication Date |
---|---|
US3996068A true US3996068A (en) | 1976-12-07 |
Family
ID=27013564
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US05/583,920 Expired - Lifetime US3996068A (en) | 1973-08-27 | 1975-06-05 | Primary dry cell |
Country Status (1)
Country | Link |
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US (1) | US3996068A (en) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4105815A (en) * | 1974-08-08 | 1978-08-08 | Polaroid Corporation | Flat battery with electrodes in slurry form |
US4929278A (en) * | 1988-01-26 | 1990-05-29 | United States Department Of Energy | Sol-gel antireflective coating on plastics |
US4966812A (en) * | 1988-01-26 | 1990-10-30 | The United States Of America As Represented By The Department Of Energy | Sol-gel antireflective coating on plastics |
US6207322B1 (en) * | 1998-11-16 | 2001-03-27 | Duracell Inc | Alkaline cell with semisolid cathode |
US6372354B1 (en) | 1999-09-13 | 2002-04-16 | Chemat Technology, Inc. | Composition and method for a coating providing anti-reflective and anti-static properties |
CN1110102C (en) * | 1995-07-19 | 2003-05-28 | 肖福平 | Non-mercury high-energy zinc-manganese cell |
US20100006524A1 (en) * | 2008-07-09 | 2010-01-14 | Brad Roach | Rotatable organizer |
CN102306758A (en) * | 2011-08-08 | 2012-01-04 | 嘉兴中科亚美合金技术有限责任公司 | Magnesium dry battery |
CN109616677A (en) * | 2018-12-10 | 2019-04-12 | 杭州长命电池有限公司 | Paste-type mercury-free battery slurry and preparation method thereof |
Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US750871A (en) * | 1904-02-02 | Exciting compound for batteries | ||
US2903498A (en) * | 1957-11-25 | 1959-09-08 | Pertrix Union Gmbh | Primary dry cell |
US3019141A (en) * | 1958-09-12 | 1962-01-30 | Pertrix Union Gmbh | Galvanic dry cell and electrolyte therefor |
US3060256A (en) * | 1960-03-07 | 1962-10-23 | Electric Storage Battery Co | Low temperature dry cell |
US3098771A (en) * | 1958-10-03 | 1963-07-23 | Pertrix Union Gmbh | Primary battery cell for high current loads and method of its manufacture |
US3306781A (en) * | 1963-06-28 | 1967-02-28 | Varta Pertrix Union Ges Mit Be | Depolarizer mixture and molded bodies |
US3345215A (en) * | 1963-03-16 | 1967-10-03 | Varta Pertrix Union Gmbh | Separator for primary cells |
US3440104A (en) * | 1965-05-14 | 1969-04-22 | Varta Pertrix Union Gmbh | Galvanic dry cells |
US3450569A (en) * | 1966-05-05 | 1969-06-17 | Us Army | Primary cell |
GB1217462A (en) | 1968-02-23 | 1970-12-31 | Hitachi Maxell | Improvements in or relating to dry cells |
US3595702A (en) * | 1968-07-16 | 1971-07-27 | Varta Gmbh | Active mass for galvanic elements and frocess of making the same |
-
1975
- 1975-06-05 US US05/583,920 patent/US3996068A/en not_active Expired - Lifetime
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US750871A (en) * | 1904-02-02 | Exciting compound for batteries | ||
US2903498A (en) * | 1957-11-25 | 1959-09-08 | Pertrix Union Gmbh | Primary dry cell |
US3019141A (en) * | 1958-09-12 | 1962-01-30 | Pertrix Union Gmbh | Galvanic dry cell and electrolyte therefor |
US3098771A (en) * | 1958-10-03 | 1963-07-23 | Pertrix Union Gmbh | Primary battery cell for high current loads and method of its manufacture |
US3060256A (en) * | 1960-03-07 | 1962-10-23 | Electric Storage Battery Co | Low temperature dry cell |
US3345215A (en) * | 1963-03-16 | 1967-10-03 | Varta Pertrix Union Gmbh | Separator for primary cells |
US3306781A (en) * | 1963-06-28 | 1967-02-28 | Varta Pertrix Union Ges Mit Be | Depolarizer mixture and molded bodies |
US3440104A (en) * | 1965-05-14 | 1969-04-22 | Varta Pertrix Union Gmbh | Galvanic dry cells |
US3450569A (en) * | 1966-05-05 | 1969-06-17 | Us Army | Primary cell |
GB1217462A (en) | 1968-02-23 | 1970-12-31 | Hitachi Maxell | Improvements in or relating to dry cells |
US3595702A (en) * | 1968-07-16 | 1971-07-27 | Varta Gmbh | Active mass for galvanic elements and frocess of making the same |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4105815A (en) * | 1974-08-08 | 1978-08-08 | Polaroid Corporation | Flat battery with electrodes in slurry form |
US4929278A (en) * | 1988-01-26 | 1990-05-29 | United States Department Of Energy | Sol-gel antireflective coating on plastics |
US4966812A (en) * | 1988-01-26 | 1990-10-30 | The United States Of America As Represented By The Department Of Energy | Sol-gel antireflective coating on plastics |
CN1110102C (en) * | 1995-07-19 | 2003-05-28 | 肖福平 | Non-mercury high-energy zinc-manganese cell |
US6207322B1 (en) * | 1998-11-16 | 2001-03-27 | Duracell Inc | Alkaline cell with semisolid cathode |
US6372354B1 (en) | 1999-09-13 | 2002-04-16 | Chemat Technology, Inc. | Composition and method for a coating providing anti-reflective and anti-static properties |
US6638630B2 (en) | 1999-09-13 | 2003-10-28 | Chemat Technology, Inc. | Composition and method for a coating providing anti-reflective and anti-static properties |
US20040028819A1 (en) * | 1999-09-13 | 2004-02-12 | Park Sung-Soon | Composition and method for a coating providing anti-reflective and anti-static properties |
US20100006524A1 (en) * | 2008-07-09 | 2010-01-14 | Brad Roach | Rotatable organizer |
CN102306758A (en) * | 2011-08-08 | 2012-01-04 | 嘉兴中科亚美合金技术有限责任公司 | Magnesium dry battery |
CN109616677A (en) * | 2018-12-10 | 2019-04-12 | 杭州长命电池有限公司 | Paste-type mercury-free battery slurry and preparation method thereof |
CN109616677B (en) * | 2018-12-10 | 2020-11-10 | 杭州长命电池有限公司 | Paste-type mercury-free battery slurry and preparation method thereof |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: MORGAN GUARANTY TRUST COMPANY OF NEW YORK, AND MOR Free format text: MORTGAGE;ASSIGNORS:UNION CARBIDE CORPORATION, A CORP.,;STP CORPORATION, A CORP. OF DE.,;UNION CARBIDE AGRICULTURAL PRODUCTS CO., INC., A CORP. OF PA.,;AND OTHERS;REEL/FRAME:004547/0001 Effective date: 19860106 |
|
AS | Assignment |
Owner name: EVEREADY BATTERY COMPANY, INC., CHECKERBOARD SQUAR Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:UNION CARBIDE CORPORATION, A CORP. OF NY;REEL/FRAME:004660/0534 Effective date: 19860630 Owner name: EVEREADY BATTERY COMPANY, INC., A CORP. OF DE., MI Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:UNION CARBIDE CORPORATION, A CORP. OF NY;REEL/FRAME:004660/0534 Effective date: 19860630 |
|
AS | Assignment |
Owner name: UNION CARBIDE CORPORATION, Free format text: RELEASED BY SECURED PARTY;ASSIGNOR:MORGAN BANK (DELAWARE) AS COLLATERAL AGENT;REEL/FRAME:004665/0131 Effective date: 19860925 |